Polyacrylonitriles Research Articles

Differentiation of photon generation depended on electrospun configuration in Eu3+/Tb3+ doped polyacrylonitrile nanofibers

Tb(acac)3 (TAH) and Eu(TTA)3Phen (ETP) doped polyacrylonitriles (PAN) have been electrospun into heterogeneous hybrid TAH/ETP/PAN and core-shell structured [(TAH/PAN)core + (ETP/PAN)shell] wire-shaped flexible nanofibers with diameter of ∼350 nm. Differential photon releasing behaviors reveal the double-color-emitting potential of Tb3+/Eu3+ combination systems and verify the effectiveness of coaxial configuration in avoiding the cross-relaxation between different rare earth ions. Luminous fluxes of the hybrid and the coaxial systems exceed 283.5 and 326.3 μlm under the excitation of 308 nm UVB-LED pump source, respectively. By adopting coaxial electrospun configuration, the color coordinates are tuned from (0.561, 0.332) in TAH/ETP/PAN to (0.435, 0.366) in [(TAH/PAN)core + (ETP/PAN)shell] fibers, which demonstrates that the core-shell structure is promising to extend the dimension of color tuning. Nanofibrosis and electrospun configurations furnish a desired approach to develop multifunctional one-dimensional nanomaterials for color displays and optoelectronic sensors.

The applications of populus fiber in removal of Cr(VI) from aqueous solution

The surface modification of natural materials to be applied in removal of Cr(VI) from aqueous solutions has attracted much attention. A natural sorbent for Cr(VI) based on natural populus fibers (PF) is prepared by transforming the cyano groups (AN) in polyacrylonitriles (PAN) grafted from PF into amidoxime groups (AO), which has strong ability to attract and chelate heavy metal ions. The prepared sorbent is characterized by Fourier Transform Infrared Spectra (FT-IR), thermogravimetric analysis (TGA), solid-state nuclear magnetic resonance (13C NMR) and scanning electron microscope (SEM). As potassium dichromate solution (K2Cr2O7) is used as a target solution for detecting adsorption capacity of the sorbent, the adsorption kinetics of the sorbent for chromiun is consistent with the pseudo-second-order kinetic model by analyzing the adsorption amount as a function of the sorbent dispersed duration in solution at pH=2. The expected adsorption mechanism is that the Cr(VI) in anionic ions Cr2O72− and HCrO4− are adsorbed through electrostatic attraction but when Cr(VI) is reduced to Cr(III) by AO, the electronegative nitrogen and oxygen in AO chelate it through coordination bond. The as-prepared PF derivant with high adsorption efficiency of chromium 180.5mg/g (3.47mmol/g), low cost, reusability and greenly preparation process suggests that the development of natural PF as a sorbent in removal of Cr(VI) from aqueous solutions is a destined significant approach.

Comprehensive Understanding of High Polar Polyacrylonitrile as an Effective Binder for Li-Ion Battery Nano-Si Anodes.

Well-defined polyacrylonitriles (PANs) with different molecular weights were synthesized through an activator regenerated by electron-transfer atom-transfer radical polymerization method and employed as binders in silicon negative electrode for lithium-ion batteries. Compared with poly(vinylidene fluoride) and carboxyl methyl cellulose as binders, the electrode performance of PANs is well-improved. Specifically, at 100 mA g(-1) from 0.01 to 1.5 V, the initial discharge capacity of PAN100-based electrode is 4147.8 mA h g(-1) and still remains about 1639.6 mA h g(-1) over 50 cycles. A comprehensive understanding on the improvement mechanism is preliminarily discussed. The results indicate that the superior performance largely depends on the higher lithium ion diffusion efficiency in PAN which results from the weak interaction between lithium ions and PAN polymer chain, and the hydrogen bonds among the nitrile group (C≡N) of PAN, Si nanoparticles, and the current collector, which will lead to an efficient coating of PAN with the Si particles and well-improved adhesion strength, synergistically depressing the structural deterioration of silicon electrodes.

Glass‐Transition Temperature (Tg) of Free‐Radically Prepared Polyacrylonitrile by Inverse Gas Chromatography, 2. Molecular‐Weight Dependence of Tg of Two Different Types of Aqueous Polymers

AbstractThe molecular‐weight dependence of the glass‐transition temperature (Tg) of a series of atactic polyacrylonitriles (PAN)s was studied by inverse gas chromatographic (IGC) analysis. PANs having different molecular weights were prepared by either; (i) the addition of isopropyl alcohol as a chain‐transfer agent, or (ii) a scission reaction induced by the addition of alkali (NaOH) to a solution (N,N‐dimethylformamide solution, at 25 °C) of the resulting polymer. The intrinsic viscosity [η] was in the range of 10.9–0.1 (dl · g−1), which corresponds to a viscosity‐averaged molecular weight (Mv) of 1 590 000–3 000. As part of the results, a side reaction, which saw the conversion of the nitrile (CN) groups of PAN into amide (CONH2) and/or carboxylic acids (COOH) groups by alkali, was found to occur. The typical molecular‐weight dependence of the Tg in free‐radically prepared PAN was discussed in connection with a chain‐transfer mechanism in an aqueous medium.Molecular‐weight dependence of the Tg for PAN (WA). An error bar is given by a short vertical arrow.magnified imageMolecular‐weight dependence of the Tg for PAN (WA). An error bar is given by a short vertical arrow.

Polymerization of acrylonitrile catalyzed by single yttrium tris(2,6‐di‐tert‐butyl‐4‐methyl phenolate)

AbstractPolymerization of acrylonitrile was carried out using yttrium tris(2,6‐di‐tert‐butyl 4‐methyl‐phenolate) (Y(OAr)3) as single component catalyst for the first time. The effects of concentrations of the monomer and catalyst, kinds of rare earth element and solvent, as well as temperature and polymerization time were investigated. The overall activation energy of polymerization in n‐hexane and THF mixture is 18.3 kJ mol−1. Polyacrylonitriles (PANs) obtained by using Y(OAr)3 in n‐hexane and THF mixture at 50 °C are predominantly atactic, while yellow PANs obtained in DMF under the same conditions have a syndiotactic‐rich configuration (>50%), and their highly branched and/or cyclized structures have also been found.© 2002 Society of Chemical Industry

Hyperlayer separation in hollow fiber flow field-flow fractionation: effect of membrane materials on resolution and selectivity

Hollow fiber flow FFF (HF FlFFF) has recently shown its capability to separate and characterize the size of submicrometer particles and has demonstrated the potential to be developed into a disposable flow FFF channel. In this work, HF FlFFF was used for the hyperlayer separation of micron-sized particles and the separation capability was examined by using various hollow fiber membrane materials (Polysulfones, cPVC, and PAN). From the experiments, PAN (polyacrylonitriles) showed an outstanding performance in particle separation compared to the other membranes. By orienting the fiber module in an upright direction, the upstream flow migration reduced band broadening of eluted peaks. When the efficiency of the PAN hollow fiber system was tested by varying the ratio of outflow-rate to radial flow-rate, it was found that optimum separation in hyperlayer HF FlFFF can be obtained at the ratio of about 6–7. From the examination of retention at or around steric inversion diameter, it was observed that experiments showed a good agreement with predictions by semi-empirical calculation. In hyperlayer HF FlFFF the diameter based selectivity values were shown to be 1.2–1.7 depending on the type of membranes and the field strength (the radial flow-rate) conditions.

Nitrile hydratase and amidase from Rhodococcus rhodochrous hydrolyze acrylic fibers and granular polyacrylonitriles.

Rhodococcus rhodochrous NCIMB 11216 produced nitrile hydratase (320 nkat mg of protein(-1)) and amidase activity (38.4 nkat mg of protein(-1)) when grown on a medium containing propionitrile. These enzymes were able to hydrolyze nitrile groups of both granular polyacrylonitriles (PAN) and acrylic fibers. Nitrile groups of PAN40 (molecular mass, 40 kDa) and PAN190 (molecular mass, 190 kDa) were converted into the corresponding carbonic acids to 1.8 and 1.0%, respectively. In contrast, surfacial nitrile groups of acrylic fibers were only converted to the corresponding amides. X-ray photoelectron spectroscopy analysis showed that 16% of the surfacial nitrile groups were hydrolyzed by the R. rhodochrous enzymes. Due to the enzymatic modification, the acrylic fibers became more hydrophilic and thus, adsorption of dyes was enhanced. This was indicated by a 15% increase in the staining level (K/S value) for C. I. Basic Blue 9.

Interpretation of the chain structures of PMMAs, PANs and PAAms obtained by using Ce(IV) and KMnO4 in combination with NTA and DTPA as initiator systems by FTIR spectroscopic analysis

Polyacrylamides (PAAms), polyacrylonitriles (PANs) and poly(methyl methacrylate)s (PMMAs) were synthesized by using Ce(NH4)2(NO3)6, Ce(SO4)2·4H2O and KMnO4 in combination with nitrilotriacetic acid (NTA) and diethylenetriamine pentaacetic acid (DTPA), which have strong chelating properties, as redox initiators. Polymerizations were carried out in the aqueous acidic solutions at 25°C and 55°C in the presence of air. The chain structures of the resulting products were studied by Fourier-transform infrared (FTIR) spectroscopic measurements. From the comparison of the spectroscopic results with gravimetric and viscometric data it was concluded that both the differences between the solubility behaviour in aqueous solutions of MMA, AN, AAm and their polymers, and catalyst–activator–monomer combinations were important parameters effecting the polymerization mechanisms, conversions and the structures of the polymers. The FTIR and viscosity results indicated that PAAms obtained in our experimental conditions formed crosslinked structures with sulphated complexes of Ce(III) and MnSO4 produced by the redox reactions between catalysts (MnO4− and Ce(IV)), NTA and AAm. Further, it was observed that PAN chains were terminated by hydrated and sulphated complexes of Ce(III) while the termination of PMMA radicals took place by primary radicals because PMMAs were formed by emulsion polymerization kinetics.

Aminated polyacrylonitrile blends with cellulose acetate

Polyacrylonitriles (PANs) were synthesized and aminated with ethylene diamine (2DA), hexamethylene diamine (6DA), and dodecane diamine (12DA), followed by blending with cellulose acetate (CA). Effects of amination and chain length of diamine on the miscibility of the aminated PAN with CA were studied. Scanning electron microscopy (SEM) micrographs of cryogenically fractured surfaces of the blends showed coarse elliptical dispersions of CA in PAN. The dispersed CA domains decreased in size with an increase in aminated PAN content. The dispersed domain size further decreased with increasing chain length of diamine. and eventually the morphology became almost homogeneous with 12DA-modified PAN blends. With increasing chain length of the diamines, the dynamic loss peak temperature of PAN in blends showed a movement toward that of CA. Fourier transform infrared (FTIR) measurements showed that the specific interaction between the aminated PAN and cellulose acetate is the hydrogen bonding between aprotic hydrogen in aminated PAN and the ester carbonyl of CA, the interactions being increased with increasing chain length of diamine.

Modified polyacrylonitrile blends with cellulose acetate: Fibers' properties

Fiber forming polyacrylonitriles (PAN) were modified by copolymerizing acrylonitrile monomer with methyl acrylate (MA) and 2-acrylamido-2-methyl propane sulfonic acid (AP), respectively, and blended with collulose acetate (CA). Fibers of MA-PAN, AP-PAN, and their blends with CA were wet-spun in dimethylformamide in a broad range of coagulation bath concentrations (CBC). The effects of hydrophilic and hydrophobic modification of PAN and the CBC, as well as the coagulation behavior, were studied in terms of morphology, mechanical properties, and water regain property of the fibers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1937–1946, 1997

Morphology of Cereal Starches Grafted with Polyacrylonitrile

AbstractMorphological aspects of six cereal starches and their graft copolymers with polyacrylonitriles (PAN) prepared from granular as well as geletinized starches are reported. Scanning electron microscopy showed that grafting is not uniform on the surface but has also occurred in the interior of the granules. The graft copolymers prepared from gelatinized starches maintained the individuality but no resemblance with original shape of the granules.

Detection of the endgroup of polyacrylonitriles by infrared spectroscopy

Detection of the endgroup of polyacrylonitriles by infrared spectroscopy